Low filled automotive polypropylene composition containing recyclates

ABSTRACT

A composition suitable for automotive application obtainable by blending at least components a) to f), or a), b), c), d), C and f) under the proviso that e) is not present a) 12 to 40 wt.-%, preferably 14 to 38 wt. %, more preferably 15 to 35 wt.-% of a first heterophasic polypropylene copolymer (HECO 1) b) 12 to 40 wt.-%, preferably 14 to 38 wt.-%, more preferably 15 to 35 wt.-% of a second heterophasic polypropylene copolymer (HECO 2) c) 15 to 65 wt.-%, preferably 18 to 60 wt.-%, more preferably 20 to 55 wt.-% of a polypropylene-polyethylene blend (A) d) 3.0 to 20 wt.-%, preferably 5.0 to 15 wt.-% and more preferably 6.0 to 15 wt.-% of an inorganic filler e) 0 to 15 wt.-% HDPE f) 0.01 to 4.0 wt.-% of additives.

FIELD OF INVENTION

The present invention relates to polypropylene based composition suitable for the automotive industry containing inorganic fillers and recyclates.

BACKGROUND

Compositions suitable for the automotive industry typically contain one or more heterophasic polypropylene copolymer(s), and/or random heterophasic copolymers, and conventionally some inorganic filler.

One of the fundamental problems in polymer business is recycling. At the moment the market for recyclates, particularly recyclates from household trash, commonly denoted PCR (‘post-consumer resins’) is somewhat limited. Starting from household trash, the sorting and separation processes employed will not allow preparing pure polymers, i.e. there will always be some contaminants, or the processes may even result in blends of different polymers. When it comes to polyolefins, which constitute the vast majority of the polymer fraction of the collected household trash, a perfect separation of polypropylene and polyethylene is hardly possible. Recycled polyolefin materials, particularly post-consumer resins, are conventionally cross-contaminated with non-polyolefin materials such as polyethylene terephthalate, polyamide, polystyrene or non-polymeric substances like wood, paper, glass or aluminum. Even worse, those post-consumer recycled polyolefin materials are readily available on a multi-ton scale but unfortunately have limited mechanical properties and frequently severe odor and/or emission problems. Apart from the required mechanical properties, the automotive industry is also very critical as far as odor and emissions are concerned, and there is a tendency to increase the requirements even further. This drastically limits the use of recyclates in automotive applications.

However, there is a deeply felt need for allowing the dumping and reuse of post-consumer polyolefin recyclates in final products without health and safety hazards.

The present invention is based on the surprising finding that sophisticated heterophasic polypropylene copolymers may be at least in part replaced by polypropylene-polyethylene blends as originating from post-consumer recycled polyolefin streams even with benefits as to VOC properties and tiger stripes performance (MSE). Surprisingly the anisotropy is not deteriorated.

SUMMARY OF THE INVENTION

The present invention provides a composition suitable for automotive application obtainable by blending at least components a) to f), or a), b), c), d), and f) under the proviso that e) is not present

a) 12 to 40 wt.-%, preferably 14 to 38 wt. %, more preferably 15 to 35 wt.-% of a first heterophasic polypropylene copolymer (HECO 1)

b) 12 to 40 wt.-%, preferably 14 to 38 wt.-%, more preferably 15 to 35 wt.-% of a second heterophasic polypropylene copolymer (HECO 2)

c) 15 to 65 wt.-%, preferably 18 to 60 wt.-%, more preferably 20 to 55 wt.-% of a polypropylene-polyethylene blend (A)

d) 3.0 to 20 wt.-%, preferably 5.0 to 15 wt.-% and more preferably 6.0 to 15 wt.-% of an inorganic filler

e) 0 to 15 wt.-% HDPE

f) 0.01 to 4.0 wt.-% of additives

whereby all percentages refer to the total composition, and whereby

-   -   the total content of polyethylene being the sum of said HDPE and         the polyethylene of said polypropylene-polyethylene blend (A)         ranges from 5.0 to 15.0 wt.-% with respect to the total         composition, and whereby

(i) the first heterophasic polypropylene copolymer (HECO 1) comprises a matrix phase and an elastomer phase dispersed therein, the first heterophasic polypropylene copolymer (HECO 1) having

-   -   a melt flow rate MFR2 (230° C., ISO1133) of 8 to 25 g/10 min,         preferably 10 to 24 g/10 min, more preferably 12 to 23 g/10 min;         and     -   an intrinsic viscosity (measured in decalin according to DIN ISO         1628/1 at 135° C.) of 3.1 dl/g to 4.5 dl/g, preferably 3.2 to         4.4 dl/g, more preferably 3.3 to 4.2 dl/g of the xylene cold         soluble fraction (XCS) content; and

(ii) the second heterophasic polypropylene copolymer (HECO 2) comprises a matrix phase and an elastomer phase dispersed therein, the second heterophasic polypropylene copolymer (HECO 2) having

-   -   a melt flow rate MFR2 (230° C., ISO1133) of 25 to 75 g/10 min,         preferably 30 to 70 g/10 min, more preferably 35 to 65 g/10 min;         and     -   an intrinsic viscosity (measured in decalin according to DIN ISO         1628/1 at 135° C.) of the xylene cold soluble fraction (XCS)         content lower than observed for HECO1, preferably 2.0 to 3.2         dl/g, more preferably 2.5 to 3.3 dl/g; and whereby

(iii) the polypropylene-polyethylene blend (A) comprises

A-1) polypropylene,

A-2) polyethylene,

wherein the weight ratio of polypropylene to polyethylene is from 19:1 to 7:3, and the polypropylene-polyethylene blend (A) having

-   -   a melt flow rate MFR2 (230° C., ISO1133) of 5.0 to 30 g/10 min,         preferably 7.0 to 26 g/10 min, more preferably 9.0 to 23 g/10         min; and     -   a xylene cold soluble fraction (XCS) of 2.0 to 15 wt.-%,         preferably of 2.5 to 13 wt. %, more preferably 3.0 to 11 wt.-%         (ISO 16152, led, 25° C.); and     -   optionally a residual ash content of below 3.0 wt.-%, preferably         0.5 to 2.7 wt.-% and more preferably 0.7 to 2.5 wt.-%,     -   and whereby the polypropylene-polyethylene blend (A) has one or         more of the following properties     -   (aa) a content of limonene as determined by using solid phase         microextraction (HS-SPME-GC-MS) of from 0.1 ppm to 100 ppm,         preferably from 0.1 ppm to 50 ppm, more preferably from 0.1 ppm         to 20 ppm, most preferably from 0.1 ppm to 5 ppm;     -   (bb) a content of fatty acid(s) as determined by using solid         phase microextraction (HS-SPME-GC-MS) of 0.1 to 100 ppm;     -   (cc) a content of polyamide(s) as determined by FTIR of 0.05 to         1.5 wt.-%;     -   (dd) a content of polystyrene(s) as determined by FTIR of 0.05         to 3.0 wt.-%;

and whereby

(iv) the inorganic filler, preferably talc,

-   -   has a median particle size d₅₀ before compounding of 0.3 to 3.0         micrometers, more preferably 0.5 to 2.5 micrometers;     -   preferably has a top-cut particle size d₉₅ before compounding of         1.0 to 8.0 micrometers, and whereby     -   the optional HDPE has a melt flow rate (190° C., ISO1133) of 1.0         to 20 g/10 min, preferably 1.0 to 10 g/10 min and     -   a density of 945 to 965 kg/m³, preferably a density of 950 to         960 kg/m³, and optionally and preferably     -   a tensile modulus (ISO 527-2) of 800 to 950 MPa,         whereby components a) to e) amount to at least 90 wt.-%,         preferably at least 95 wt.-%, most preferably at least 96 wt.-%         of said composition suitable for automotive application.

The present invention further provides an article comprising, preferably consisting of the composition as described herein.

In a further aspect, the present invention provides the use of the composition according to the present invention for injection molding of articles.

Specifically, the present invention provides a composition suitable for automotive application as described above obtainable by blending at least components a) to f), or a), b), c), d), and f) under the proviso that e) is not present

a) 12 to 40 wt.-%, preferably 14 to 38 wt. %, more preferably 15 to 35 wt.-% of a first heterophasic polypropylene copolymer (HECO 1)

b) 12 to 40 wt.-%, preferably 14 to 38 wt.-%, more preferably 15 to 35 wt.-% of a second heterophasic polypropylene copolymer (HECO 2)

c) 15 to 65 wt.-%, preferably 18 to 60 wt.-%, more preferably 20 to 55 wt.-% of a polypropylene-polyethylene blend (A)

d) 3.0 to 20 wt.-%, preferably 5.0 to 15 wt.-% and more preferably 6.0 to 15 wt.-% of an inorganic filler

e) 0 to 15 wt.-% HDPE

f) 0.01 to 4.0 wt.-% of additives

-   -   whereby all percentages refer to the total composition, whereby     -   the total content of polyethylene being the sum of said HDPE and         the polyethylene of said polypropylene-polyethylene blend (A)         ranges from 5.0 to 15.0 wt.-% with respect to the total         composition, and whereby         and whereby

(i) the first heterophasic polypropylene copolymer (HECO 1) comprises a matrix phase and an elastomer phase dispersed therein, the first heterophasic polypropylene copolymer (HECO 1) having

-   -   melt flow rate MFR2 (230° C., ISO1133) of 8 to 25 g/10 min,         preferably 10 to 24 g/10 min, more preferably 12 to 23 g/10 min;         and     -   an intrinsic viscosity (measured in decalin according to DIN ISO         1628/1 at 135° C.) of 3.1 dl/g to 4.5 dl/g, preferably 3.2 to         4.4 dl/g, more preferably 3.3 to 4.2 dl/g of the xylene cold         soluble fraction (XCS) content; and     -   a xylene cold soluble fraction (XCS) of 19 to 40 wt.-%,         preferably of 20 to 37 wt. %, more preferably 22 to 35 wt.-%         (ISO 16152, led, 25° C.); and     -   a melt flow rate MFR2 (230° C., ISO1133) of 20 to 50 g/10 min,         preferably 25 to 45 g/10 min, more preferably 28 to 44 g/10 min         of the xylene insoluble fraction (XCI) (ISO 16152, led, 25° C.),     -   a content of units derived from ethylene in the xylene cold         soluble fraction (XCS) of 40 to 60 wt.-%, preferably of 41 to 55         wt. %, more preferably 42 to 50 wt.-%, and whereby

(ii) the second heterophasic polypropylene copolymer (HECO 2) comprises a matrix phase and an elastomer phase dispersed therein, the second heterophasic polypropylene copolymer (HECO 2) having

-   -   a melt flow rate MFR2 (230° C., ISO1133) of 25 to 75 g/10 min,         preferably 30 to 70 g/10 min, more preferably 35 to 65 g/10 min;         and     -   an intrinsic viscosity (measured in decalin according to DIN ISO         1628/1 at 135° C.) of the xylene cold soluble fraction (XCS)         content lower than observed for HECO1, preferably 2.0 to 3.2         dl/g, more preferably 2.5 to 3.3 dl/g; and     -   a xylene cold soluble fraction (XCS) of 8 to 18 wt.-%,         preferably of 10 to 17 wt. %, more preferably 12 to 17 wt.-%         (ISO 16152, led, 25° C.); and     -   a melt flow rate MFR2 (230° C., ISO1133) of 50 to 200 g/10 min,         preferably 60 to 180 g/10 min, more preferably 70 to 160 g/10         min of the xylene insoluble fraction (XCI) (ISO 16152, led, 25°         C.), and     -   a content of units derived from ethylene in the xylene cold         soluble fraction (XCS) of 25 to 44 wt.-%, preferably of 30 to 42         wt. %, more preferably 35 to 40 wt.-%, and

(iii) the polypropylene-polyethylene blend (A) comprises

A-1) polypropylene,

A-2) polyethylene,

wherein the weight ratio of polypropylene to polyethylene is from 19:1 to 7:3, and the polypropylene-polyethylene blend (A) has

-   -   a melt flow rate MFR2 (230° C., ISO1133) of 5.0 to 30 g/10 min,         preferably 7.0 to 26 g/10 min, more preferably 9.0 to 23 g/10         min; and     -   a xylene cold soluble fraction (XCS) of 2.0 to 15 wt.-%,         preferably of 2.5 to 13 wt. %, more preferably 3.0 to 11 wt.-%         (ISO 16152, led, 25° C.); and     -   optionally a residual ash content of below 3.0 wt.-%, preferably         0.5 to 2.7 wt.-% and more preferably 0.7 to 2.5 wt.-%,     -   and whereby the polypropylene-polyethylene blend (A) has one or         more of the following properties     -   (aa) a content of limonene as determined by using solid phase         microextraction (HS-SPME-GC-MS) of from 0.1 ppm to 100 ppm,         preferably from 0.1 ppm to 50 ppm, more preferably from 0.1 ppm         to 20 ppm, most preferably from 0.1 ppm to 5 ppm;     -   (bb) a content of fatty acid(s) as determined by using solid         phase microextraction (HS-SPME-GC-MS) of 0.1 to 100 ppm;     -   (cc) a content of polyamide(s) as determined by FTIR of 0.05 to         1.5 wt.-%;     -   (dd) a content of polystyrene(s) as determined by FTIR of 0.05         to 3.0 wt.-%;     -   and whereby

(iv) the inorganic filler, preferably talc

-   -   has a median particle size d₅₀ before compounding of 0.3 to 3.0         micrometers, more preferably 0.5 to 2.5 micrometers; and     -   preferably has a top cut particle size d₉₅ before compounding of         1.0 to 8.0 micrometers.     -   and whereby     -   the optional HDPE has a melt flow rate (190° C., ISO1133) of 1.0         to 20 g/10 min, preferably 1.0 to 10 g/10 min, and     -   a density of 945 to 965 kg/m³, preferably a density of 950 to         960 kg/m³, and optionally but also preferably     -   a tensile modulus (ISO527-2) of 800 to 950 MPa,

whereby components a) to e) amount to at least 90 wt.-%, preferably at least 95 wt.-%, most preferably at least 96 wt.-% of said composition suitable for automotive applications.

The composition according to the present invention preferably has a tensile modulus (ISO 527.2; 23° C.) of 1650 to 1900 MPa.

Advantages

The present invention not only allows the replacement of sophisticated heterophasic propylene copolymers by recycled polypropylene-polyethylene blends originating from household trash being available in very large scale but also enables improvements as to tiger stripe performance as reflected by MSE value and VOC (VDA 278) properties. In addition to that anisotropy turned out to stay the same, although it was commonly assumed shrinkage and anisotropy will get worse when introducing a recycling polyolefin blend.

Definitions

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention pertains. Although, any methods and materials similar or equivalent to those described herein can be used in practice for testing of the present invention, the preferred materials and methods are described herein. In describing and claiming the present invention, the following terminology will be used in accordance with the definitions set out below. Unless clearly indicated otherwise, use of the terms “a,” “an,” and the like refers to one or more. For the purposes of the present description, the term “recycled waste” or “recycled material” is used to indicate a material recovered from both post-consumer waste and industrial waste, as opposed to virgin polymers. Post-consumer waste refers to objects having completed at least a first use cycle (or life cycle), i.e. having already served their first purpose. In contrast to that, industrial waste refers to manufacturing scrap, respectively conversion scrap, which does not normally reach a consumer. The term “virgin” denotes the newly produced materials and/or objects prior to their first use, which have not already been recycled. Virgin materials and post-consumer materials can be differentiated easily based on absence or presence of contaminants such as limonene and/or fatty acids and/or paper and/or wood. Polypropylene-polyethylene blends can also be differentiated with respect to their origin by presence of polystyrene and/or polyamide. Residual content denotes a content above the detection limit. Many different kinds of polyethylene or polypropylene can be present in “recycled material”. The ratio polypropylene (A-1) versus polyethylene plus polyethylene copolymer (A-2) is determined experimentally by using isotactic polypropylene (iPP) and high density polyethylene (HDPE) for calibration. A polymer blend is a mixture of two or more polymeric components. In general, the blend can be prepared by mixing the two or more polymeric components. A suitable mixing procedures known in the art is post-polymerization blending. Post-polymerization blending can be dry blending of polymeric components such as polymer powders and/or compounded polymer pellets or melt blending by melt mixing the polymeric components. A propylene random copolymer is a copolymer of propylene monomer units and comonomer units in which the comonomer units are distributed randomly over the polypropylene chain. A “compatibilizer” is a substance in polymer chemistry, which is added to a blend of polymers with limited miscibility in order to increase their stability. “Polypropylene-polyethylene blend” refers to a composition containing both polypropylene and polyethylene including also polypropylene copolymers as well as polyethylene copolymers. As a direct determination of the polypropylene content and polyethylene content is not possible, the weight ratio polypropylene (A-1) to polyethylene (A-2) of 19:1 to 7:3 denotes the equivalent ratio as determined from calibration by iPP and HDPE and determination by IR spectroscopy. The term “elastomer” denotes a natural or synthetic polymer having elastic properties. The term “XCS” refers to the xylene cold soluble fraction (XCS wt.-%) determined at 25° C. according to ISO 16152. The term “XCI” refers to the xylene cold insoluble fraction (XCI wt.-%) determined at 25° C. according to ISO 16152. If not indicated otherwise “%” refers to weight-%. The presence of a heterophasic nature can be easily determined by the number of glass transition points. Reactor blend is a blend originating from the production in two or more reactors coupled in series or in a reactor having two or more reaction compartments. A reactor blend may alternatively result from blending in solution. A reactor blend stands in contrast to a compound as produced by melt extrusion. Ethylene based elastomer means a elastomer being composed of units derived from ethylene in an amount of at least wt.-%.

Inventive Compositions

The composition suitable for automotive application according to the present invention is particularly suitable for injection molding of articles to be used in the interior and exterior of vehicles.

The composition suitable for automotive application according to the present invention has one or more of the following characteristics:

-   -   (aa) residual amounts of limonene;     -   (bb) residual content of fatty acid(s);     -   (cc) residual content of polyamide(s);     -   (dd) residual content of polystyrene(s).

These residual amounts are introduced via the incorporation of the polypropylene-polyethylene blend (A), with the polypropylene-polyethylene blend (A) originating from consumer trash. The presence of such residual materials can be used as way of differentiating the incorporation of a polypropylene-polyethylene blend (A) originating from consumer trash versus the incorporation of polypropylene-polyethylene blend (A) originating from industrial trash. In other words, the above allows to differentiate into post-consumer recyclates (PCR) and post-industrial recyclates (PIR). The measurement of the residual amounts of limonene/fatty acid, polyamide and/or polystyrene can be carried out on the final composition and also can be carried out on blend (A).

The composition suitable for automotive application according to the present invention preferably has a VOC as measured on the material as obtained directly from the extrusion following the procedure as described in VDA278 of less than 75 μg per gram of composition, preferably less than 70 μg per gram of composition. Without being want to be bound by theory, the applicant believes that in a first aspect the presence of filler, particularly the presence of talc is beneficial. In a second aspect, the incorporation of polypropylene-polyethylene blend (A) may also contribute to the overall surprisingly low VOC content as the polymers may have lost some amounts of VOC over their first use because of being subjected to the elements, i.e. higher temperatures together with wind. In any case, lower VOC contents, i.e. lower than 70 μg per gram of composition (VDA 278) are obtainable by relatively high amounts of blend (A), particularly by 30 to 60 wt.-%, preferably 35 to 55 wt.-%, more preferably 45 to 55 wt.-% of the polypropylene-polyethylene blend (A).

The composition according to the present invention comprises a total content of polyethylene, which is the sum of said HDPE and the polyethylene of said polypropylene-polyethylene blend (A) ranging from 5.0 to 15.0 wt.-%, preferably 6.0 to 12.0 wt.-%, with respect to the total composition.

The composition according to the present invention preferably has a tensile modulus (ISO 527.2; 23° C.) of 1650 to 1900 MPa.

The composition according to the present invention preferably has melt flow rate (ISO 1133, 2.16 kg, 230° C.) of 13.0 to 25 g/10 min.

The composition according to the present invention preferably has a MSE surface quality of below 4.5. Such excellent surface quality is obtained when the amount of blend (A) is rather low, preferably 15 to 30 wt.-%, more preferably 18 to 30 wt.-%, most preferably 20 to 30 wt.-%.

The composition suitable for automotive application according to the present invention preferably has a heat deflection temperature (ISO 75 B) of at least 90° C.

HECO 1

The first heterophasic polypropylene copolymer (HECO 1) comprises a matrix phase and an elastomer phase dispersed therein, whereby the first heterophasic polypropylene copolymer (HECO 1) has a melt flow rate MFR2 (230° C., ISO1133) of 8 to 25 g/10 min, preferably 10 to 24 g/10 min, more preferably 12 to 23 g/10 min; and an intrinsic viscosity (measured in decalin according to DIN ISO 1628/1 at 135° C.) of 3.1 dl/g to 4.5 dl/g, preferably 3.2 to 4.4 dl/g, more preferably 3.3 to 4.2 dl/g of the xylene cold soluble fraction (XCS).

Preferably the first heterophasic polypropylene copolymer (HECO 1) comprises a matrix phase and an elastomer phase dispersed therein, whereby the first heterophasic polypropylene copolymer (HECO 1) has

-   -   melt flow rate MFR2 (230° C., ISO1133) of 8 to 25 g/10 min,         preferably 10 to 24 g/10 min, more preferably 12 to 23 g/10 min;         and     -   an intrinsic viscosity (measured in decalin according to DIN ISO         1628/1 at 135° C.) of 3.1 dl/g to 4.5 dl/g, preferably 3.2 to         4.4 dl/g, more preferably 3.3 to 4.2 dl/g of the xylene cold         soluble fraction (XCS) content; and     -   a xylene cold soluble fraction (XCS) of 19 to 40 wt.-%,         preferably of 20 to 37 wt. %, more preferably 22 to 35 wt.-%         (ISO 16152, led, 25° C.); and     -   a melt flow rate MFR2 (230° C., ISO1133) of 20 to 50 g/10 min,         preferably 25 to 45 g/10 min, more preferably 28 to 44 g/10 min         of the xylene insoluble fraction (XCI) (ISO 16152, led, 25° C.),         and     -   a content of units derived from ethylene in the xylene cold         soluble fraction (XCS) of 40 to 60 wt.-%, preferably of 41 to 55         wt. %, more preferably 42 to 50 wt.-%.

The first heterophasic polypropylene copolymer (HECO 1) preferably is nucleated, more preferably is nucleated by poly(vinylcyclohexane).

Heterophasic polypropylene copolymer of such nature are commercially available.

HECO2

The second heterophasic polypropylene copolymer (HECO 2) comprises a matrix phase and an elastomer phase dispersed therein, whereby the second heterophasic polypropylene copolymer (HECO 2) has

-   -   a melt flow rate MFR2 (230° C., ISO1133) of 25 to 75 g/10 min,         preferably 30 to 70 g/10 min, more preferably 35 to 65 g/10 min;         and     -   an intrinsic viscosity (measured in decalin according to DIN ISO         1628/1 at 135° C.) of the xylene cold soluble fraction (XCS)         content lower than observed for HECO1, preferably 2.0 to 3.2         dl/g, more preferably 2.5 to 3.3 dl/g.

Preferably the second heterophasic polypropylene copolymer (HECO 2) comprises a matrix phase and an elastomer phase dispersed therein, whereby the second heterophasic polypropylene copolymer (HECO 2) has

-   -   a melt flow rate MFR2 (230° C., ISO1133) of 25 to 75 g/10 min,         preferably 30 to 70 g/10 min, more preferably 35 to 65 g/10 min;         and     -   an intrinsic viscosity (measured in decalin according to DIN ISO         1628/1 at 135° C.) of the xylene cold soluble fraction (XCS)         content lower than observed for HECO1, preferably 2.0 to 3.2         dl/g, more preferably 2.5 to 3.3 dl/g; and     -   a xylene cold soluble fraction (XCS) of 8 to 18 wt.-%,         preferably of 10 to 17 wt. %, more preferably 12 to 17 wt.-%         (ISO 16152, led, 25° C.); and     -   a melt flow rate MFR2 (230° C., ISO1133) of 50 to 200 g/10 min,         preferably 60 to 180 g/10 min, more preferably 70 to 160 g/10         min of the xylene insoluble fraction (XCI) (ISO 16152, led, 25°         C.), and     -   a content of units derived from ethylene in the xylene cold         soluble fraction (XCS) of 25 to 44 wt.-%, preferably of 30 to 42         wt. %, more preferably 35 to 40 wt.-%. Such heterophasic         propylene copolymer are commercially available.

Polypropylene-polyethylene Blend (A)

The polypropylene-polyethylene blend (A) according to present invention comprises

A-1) polypropylene,

A-2) polyethylene,

wherein the weight ratio of polypropylene to polyethylene is from 19:1 to 7:3.

Simultaneously the polypropylene-polyethylene blend (A) has

-   -   a melt flow rate MFR2 (230° C., ISO1133) of 5.0 to 30 g/10 min,         preferably 7.0 to 26 g/10 min, more preferably 9.0 to 23 g/10         min; and     -   a xylene cold soluble fraction (XCS) of 2.0 to 15 wt.-%,         preferably of 2.5 to 13 wt. %, more preferably 3.0 to 11 wt.-%         (ISO 16152, led, 25° C.); and     -   optionally a residual ash content of below 3.0 wt.-%, preferably         0.5 to 2.7 wt.-% and more preferably 0.7 to 2.5 wt.-%.

The polypropylene-polyethylene blend (A) according to present invention is a recycled material, preferably originates from household trash. It is particularly preferred that the polypropylene-polyethylene blend (A) according to present invention originates in an amount of at least 90 wt.-% from post-consumer waste.

The polypropylene-polyethylene blend (A) according to present invention may have one or more of the following properties

aa) a content of limonene as determined by using solid phase microextraction (HS-SPME-GC-MS) of from 0.1 ppm to 100 ppm, preferably from 0.1 ppm to 50 ppm, more preferably from 0.1 ppm to 20 ppm, most preferably from 0.1 ppm to 5 ppm;

bb) a content of fatty acid(s) as determined by using solid phase microextraction (HS-SPME-GC-MS) of 0.1 to 100 ppm;

cc) a content of polyamide(s) as determined by NMR of 0.05 to 1.5 wt.-%;

dd) a content of polystyrene(s) as determined by NMR of 0.05 to 3.0 wt.-%;

ee) a residual ash content of mentioned above.

It should be understood that the polypropylene-polyethylene blend (A) may vary broadly in composition, i.e. may include polypropylene homopolymer, polypropylene copolymer, polyethylene, and polyethylene copolymers. As a direct determination of the polypropylene content and polyethylene content is not possible, the weight ratio polypropylene (A-1) to polyethylene (A-2) is 19:1 to 7:3 is the equivalent ratio as determined from calibration by iPP and HDPE.

Conventionally the polypropylene-polyethylene blend (A) according to the present invention may also have one or more of the following:

-   -   residual content of PET determined as described in the         experimental part;     -   residual talc and chalk content as described in the experimental         part;     -   residual content of metals (determined by x ray fluorescence         (XRF)     -   residual amount of paper as described in the experimental part     -   residual amount of wood as described in the experimental part     -   total free fatty acid content of 0.1 to 100 ppm as measured by         using headspace solid phase micro-extraction (HS-SPME-GC-MS).

The polypropylene-polyethylene blend (A) according to the present invention is preferably obtained from washing and/or aeration steps as known in the art.

Additives

Additives are commonly used in the composition according to the present invention. Preferably, the additives are selected from one or more of antioxidant(s), UV stabilizer(s), slip agent(s), nucleating agent(s), pigment(s), lubricant(s), masterbatch polymer(s) and/or anti-fogging agents.

Inorganic Filler

The inorganic filler is preferably talc. The inorganic filler, preferably talc has a median particle size d₅₀ before compounding of 0.3 to 3.0 micrometers, more preferably 0.5 to 2.5 micrometers; and preferably has a top-cut particle size d₉₅ before compounding of 1.0 to 8.0 micrometers. Such inorganic fillers are commercially available.

HDPE

HDPE, particularly virgin HDPE may be added into the composition according to the present invention in amounts of up to 15 wt.-%. HDPE contributes to the scratch resistance of the final composition. Due to the presence of HDPE in blend (A), the amount of HDPE for a target scratch resistance may be reduced or may be omitted completely.

DETAILED DESCRIPTION

In the following, several preferred embodiments shall be described.

In a first preferred embodiment, the composition suitable for automotive application according to the present invention is obtainable by blending at least components a) to f), or a), b), c), d), and f) under the proviso that e) is not present

a) 20 to 40 wt.-%, preferably 20 to 38 wt. %, more preferably 20 to 35 wt.-% of the first heterophasic polypropylene copolymer (HECO 1)

b) 20 to 40 wt.-%, preferably 20 to 38 wt.-%, more preferably 20 to 35 wt.-% of the second heterophasic polypropylene copolymer (HECO 2)

c) 15 to 30 wt.-%, preferably 18 to 30 wt.-%, more preferably 20 to 30 wt.-% of the polypropylene-polyethylene blend (A)

d) 3.0 to 20 wt.-%, preferably 5.0 to 15 wt.-% and more preferably 6.0 to 15 wt.-% of the inorganic filler

e) 0 to 15 wt.-% HDPE

f) 0.01 to 4.0 wt.-% of additives

whereby components a) to e) amount to at least 90 wt.-%, preferably at least 95 wt.-%, most preferably at least 96 wt.-% of said composition suitable for automotive application.

In this embodiment the amount of blend (A) is rather low, i.e. the amount of recyclate which can be dumped in the final product is not that high. However, the MSE surface quality is surprisingly excellent and the VOC is also good in this embodiment. All definitions and preferred aspect for the individual components as described above, particularly for blend (A) also hold for this embodiment.

Thus, the composition according to this embodiment preferably has a MSE surface quality of below 4.5.

In another embodiment, the composition suitable for automotive application according to the present invention is obtainable by blending at least components a) to f), or a), b), c), d), and f) under the proviso that e) is not present

a) 10 to 20 wt.-%, preferably 11 to 20 wt. %, more preferably 12 to 20 wt.-% of the first heterophasic polypropylene copolymer (HECO 1)

b) 10 to 20 wt.-%, preferably 11 to 20 wt.-%, more preferably 12 to 20 wt.-% of the second heterophasic polypropylene copolymer (HECO 2)

c) 30 to 60 wt.-%, preferably 35 to 55 wt.-%, more preferably 45 to 55 wt.-% of the polypropylene-polyethylene blend (A)

d) 3.0 to 20 wt.-%, preferably 5.0 to 15 wt.-% and more preferably 6.0 to 15 wt.-% of the inorganic filler

e) 0 to 15 wt.-% HDPE

f) 0.01 to 4.0 wt.-% of additives

whereby components a) to e) amount to at least 90 wt.-%, preferably at least 95 wt.-%, most preferably at least 96 wt.-% of said composition suitable for automotive application.

In this second embodiment the amount of polypropylene-polyethylene blend (A), i.e. of the recyclate is maximized. This allows dumping of higher amounts of recyclates in the final products.

All definitions and preferred aspect for the individual components as described above, particularly for blend (A) also hold for this embodiment.

The composition according to the second embodiment preferably has a VOC as measured on the material as obtained directly from the extrusion following the procedure as described in VDA278 of less than 70 g per gram of composition.

Experimental Section

The following Examples are included to demonstrate certain aspects and embodiments of the invention as described in the claims. It should be appreciated by those of skill in the art, however, that the following description is illustrative only and should not be taken in any way as a restriction of the invention.

Test Methods

a) Amount of iPP, Polystyrene, Polyethylene (and Ethylene Containing

Copolymers), Poly(Ethylene Terephthalate), and Amount of Polyamide-6 To establish different calibration curves different standards, iPP and HDPE and iPP, PS and PA6 were blended. For the quantification of the content of the foreign polymers, IR spectra were recorded in the solid-state using a Bruker Vertex 70 FTIR spectrometer. Films were prepared with a compression-molding device at 190° C. with 4-6 MPa clamping force. The thickness of the films for the calibration standards for iPP and HDPE was 300 μm and for the quantification of the iPP, PS and PA 6 50-100 μm film thickness was used. Standard transmission FTIR spectroscopy is employed using a spectral range of 4000-400 cm−1, an aperture of 6 mm, a spectral resolution of 2 cm−1, 16 background scans, 16 spectrum scans, an interferogram zero filling factor of 32 and Norton Beer strong apodization.

The absorption of the band at 1167 cm−1 in iPP is measured and the iPP content is quantified according to a calibration curve (absorption/thickness in cm versus iPP content in weight %).

The absorption of the band at 1601 cm−1 (PS) and 3300 cm−1 (PA6) are measured and the PS and PA6 content quantified according to the calibration curve (absorption/thickness in cm versus PS and PA content in wt.-%). The content of polyethylene and ethylene containing copolymers is obtained by subtracting (iPP+PS+PA6) from 100, taking into account the content of non-polymeric impurities as determined in the methods below. The analysis is performed as a double determination.

b) Tensile Modulus and Tensile Strain at Break

were measured according to ISO 527-2 (cross head speed=1 mm/min; test speed 50 mm/min at 23° C.) using injection molded specimens 1 B prepared as described in EN ISO 1873-2 (dog bone shape, 4 mm thickness). The measurement was done after 96 h conditioning time at 23° C. of the specimen.

c) The Impact Strength

was determined as Charpy Notched Impact Strength according to ISO 179-1 eA at +23° C., at 0° C., and at −20° C. on injection molded specimens of 80×10×4 mm³ prepared according to EN ISO 1873-2. The measurement was done after 96 h conditioning time at 23° C. of the specimen.

d) Instrumented Puncture Test

Instrumented puncture test was performed on 60×60×1 mm³ injection-molded plaques at 23° C., 0° C. and −20° C. according to ISO6603-2:2000. The measurement was done after 96 h conditioning time at 23° C. of the specimen.

e) Comonomer Content

Poly(Propylene-Co-Ethylene)—Ethylene Content—IR Spectroscopy Quantitative infrared (IR) spectroscopy was used to quantify the ethylene content of the poly(ethylene-co-propene) copolymers through calibration to a primary method. Calibration was facilitated through the use of a set of in-house non-commercial calibration standards of known ethylene contents determined by quantitative ¹³C solution-state nuclear magnetic resonance (NMR) spectroscopy. The calibration procedure was undertaken in the conventional manner well documented in the literature. The calibration set consisted of 38 calibration standards with ethylene contents ranging 0.2-75.0 wt. % produced at either pilot or full scale under a variety of conditions. The calibration set was selected to reflect the typical variety of copolymers encountered by the final quantitative IR spectroscopy method.

Quantitative IR spectra were recorded in the solid-state using a Bruker Vertex 70 FTIR spectrometer. Spectra were recorded on 25×25 mm square films of 300 μm thickness prepared by compression moulding at 180-210° C. and 4-6 MPa. For samples with very high ethylene contents (>50 mol %) 100 μm thick films were used. Standard transmission FTIR spectroscopy was employed using a spectral range of 5000-500 cm⁻¹, an aperture of 6 mm, a spectral resolution of 2 cm⁻¹, 16 background scans, 16 spectrum scans, an interferogram zero filling factor of 64 and Blackmann-Harris 3-term apodisation. Quantitative analysis was undertaken using the total area of the CH₂ rocking deformations at 730 and 720 cm⁻¹ (A_(Q)) corresponding to (CH₂)_(>2) structural units (integration method G, limits 762 and 694 cm⁻¹). The quantitative band was normalised to the area of the CH band at 4323 cm⁻¹ (A_(R)) corresponding to CH structural units (integration method G, limits 4650, 4007 cm⁻¹). The ethylene content in units of weight percent was then predicted from the normalised absorption (A_(Q)/A_(R)) using a quadratic calibration curve. The calibration curve having previously been constructed by ordinary least squares (OLS) regression of the normalised absorptions and primary comonomer contents measured on the calibration set.

Poly(Propylene-Co-Ethylene)—Ethylene Content—¹³C NMR Spectroscopy

Quantitative ¹³C{¹H} NMR spectra were recorded in the solution-state using a Bruker Avance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for ¹H and ¹³C respectively. All spectra were recorded using a ¹³C optimised 10 mm extended temperature probehead at 125° C. using nitrogen gas for all pneumatics. Approximately 200 mg of material was dissolved in 3 ml of 1,2-tetrachloroethane-d₂ (TCE-d₂) along with chromium (III) acetylacetonate (Cr(acac)₃) resulting in a 65 mM solution of relaxation agent in solvent (Singh, G., Kothari, A., Gupta, V., Polymer Testing 28 5 (2009), 475). To ensure a homogenous solution, after initial sample preparation in a heat block, the NMR tube was further heated in a rotatory oven for at least 1 hour. Upon insertion into the magnet the tube was spun at 10 Hz. This setup was chosen primarily for the high resolution and quantitatively needed for accurate ethylene content quantification. Standard single-pulse excitation was employed without NOE, using an optimised tip angle, 1 s recycle delay and a bi-level WALTZ16 decoupling scheme (Zhou, Z., et al. J. Mag. Reson. 187 (2007) 225, and in Busico, V., et al, Macromol. Rapid Commun. 2007, 28, 1128). A total of 6144 (6k) transients were acquired per spectra. Quantitative ¹³C{¹H}NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals. All chemical shifts were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm using the chemical shift of the solvent. This approach allowed comparable referencing even when this structural unit was not present. Characteristic signals corresponding to the incorporation of ethylene were observed (Cheng, H. N., Macromolecules 17 (1984), 1950) and the comonomer fraction calculated as the fraction of ethylene in the polymer with respect to all monomer in the polymer: fE=(E/(P+E) The comonomer fraction was quantified using the method of Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157) through integration of multiple signals across the whole spectral region in the ¹³C{¹H} spectra. This method was chosen for its robust nature and ability to account for the presence of regio-defects when needed. Integral regions were slightly adjusted to increase applicability across the whole range of encountered comonomer contents. For systems with very low ethylene content where only isolated ethylene in PPEPP sequences were observed the method of Wang et. al. was modified reducing the influence of integration of sites that are no longer present. This approach reduced the overestimation of ethylene content for such systems and was achieved by reduction of the number of sites used to determine the absolute ethylene content to E=0.5(Sββ+Sβγ+Sβδ+0.5(Sαβ+Sαγ)) Through the use of this set of sites the corresponding integral equation becomes E=0.5(I_(H)+I_(G)+0.5(I_(C)+ID)) using the same notation used in the article of Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157). Equations used for absolute propylene content were not modified. The mole percent comonomer incorporation was calculated from the mole fraction: E [mol %]=100*fE. The weight percent comonomer incorporation was calculated from the mole fraction: E [wt. %]=100*(fE*28.06)/((fE*28.06)+((1−fE)*42.08)).

f) Comonomer Content

Contents were determined using a film thickness method using the intensity of the quantitative band I(q) and the thickness of the pressed film T using the following relationship: [I(q)/T]m+c=C where m and c are the coefficients determined from the calibration curve constructed using the comonomer contents obtained from ¹³C-NMR spectroscopy.

Comonomer content was measured in a known manner based on Fourier transform infrared spectroscopy (FTIR) calibrated with ¹³C-NMR, using Nicolet Magna 550 IR spectrometer together with Nicolet Omnic FTIR software. Films having a thickness of about 250 μm were compression molded from the samples. Similar films were made from calibration samples having a known content of the comonomer. The comonomer content was determined from the spectrum from the wave number range of from 1430 to 1100 cm⁻¹. The absorbance was measured as the height of the peak by selecting the so-called short or long base line or both. The short base line was drawn in about 1410-1320 cm⁻¹ through the minimum points and the long base line about between 1410 and 1220 cm⁻¹. Calibrations needed to be done specifically for each base line type. Also, the comonomer content of the unknown sample was within the range of the comonomer contents of the calibration samples.

g) Talc and Chalk Content

TGA According to the Following Procedure:

Thermogravimetric Analysis (TGA) experiments were performed with a Perkin Elmer TGA 8000. Approximately 10-20 mg of material was placed in a platinum pan. The temperature was equilibrated at 50° C. for 10 minutes, and afterwards raised to 950° C. under nitrogen at a heating rate of 20° C./min. The weight loss between ca. 550° C. and 700° C. (WCO₂) was assigned to CO₂ evolving from CaCOO₃, and therefore the chalk content was evaluated as:

Chalk content=100/44×WCO2

Afterwards the temperature was lowered to 300° C. at a cooling rate of 20° C./min. Then the gas was switched to oxygen, and the temperature was raised again to 900° C. The weight loss in this step was assigned to carbon black (Wcb). Knowing the content of carbon black and chalk, the ash content excluding chalk and carbon black was calculated as:

Ash content=(Ash residue)−56/44×WCO2−Wcb

Where Ash residue is the weight % measured at 900° C. in the first step conducted under nitrogen. The ash content is estimated to be the same as the talc content for the investigated recyclates.

h) MFR

Melt flow rates were measured with a load of 2.16 kg (MFR₂) at 230° C. (polypropylene based materials) or at 190° C. (polyethylene based materials). The melt flow rate is that quantity of polymer in grams which the test apparatus standardized to ISO 1133 extrudes within 10 minutes at a temperature of 230° C. (or 190° C.) under a load of 2.16 kg.

i) Amount of Metals

was determined by x ray fluorescence (XRF)

j) Amount of Paper, Wood

Paper and wood were determined by conventional laboratory methods including milling, floatation, microscopy and Thermogravimetric Analysis (TGA).

k) Limonene Measurement

Limonene quantification was carried out using solid phase microextraction (HS-SPME-GC-MS) by standard addition.

50 mg ground samples were weighed into 20 mL headspace vials and after the addition of limonene in different concentrations and a glass-coated magnetic stir bar. the vial was closed with a magnetic cap lined with silicone/PTFE. Micro capillaries (10 pL) were used to add diluted limonene standards of known concentrations to the sample. Addition of 0, 2, 20 and 100 ng equals 0 mg/kg, 0.1 mg/kg, 1 mg/kg and 5 mg/kg limonene, in addition standard amounts of 6.6 mg/kg, 11 mg/kg and 16.5 mg/kg limonene were used in combination with some of the samples tested in this application. For quantification, ion-93 acquired in SIM mode was used. Enrichment of the volatile fraction was carried out by headspace solid phase microextraction with a 2 cm stable flex 50/30 μm DVB/Carboxen/PDMS fibre at 60° C. for 20 minutes. Desorption was carried out directly in the heated injection port of a GCMS system at 270° C.

GCMS Parameters:

Column: 30 m HP 5 MS 0.25*0.25

Injector: Splitless with 0.75 mm SPME Liner, 270° C.

Temperature program: −10° C. (1 min)

Carrier gas: Helium 5.0, 31 cm/s linear velocity, constant flow

MS: Single quadrupole, direct interface, 280° C. interface temperature

Acquisition: SIM scan mode

Scan parameter: 20-300 amu

SIM Parameter: m/Z 93, 100 ms dwell time

l) Total Free Fatty Acid Content

Fatty acid quantification was carried out using headspace solid phase micro-extraction (HS-SPME-GC-MS) by standard addition.

50 mg ground samples were weighed in 20 mL headspace vial and after the addition of limonene in different concentrations and a glass coated magnetic stir bar the vial was closed with a magnetic cap lined with silicone/PTFE. 10 μL Micro-capillaries were used to add diluted free fatty acid mix (acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid and octanoic acid) standards of known concentrations to the sample at three different levels. Addition of 0, 50, 100 and 500 ng equals 0 mg/kg, 1 mg/kg, 2 mg/kg and 10 mg/kg of each individual acid. For quantification ion 60 acquired in SIM mode was used for all acids except propanoic acid, here ion 74 was used.

GCMS Parameter:

Column: 20 m ZB Wax plus 0.25*0.25

Injector: Split 5:1 with glass lined split liner, 250° C.

Temperature program: 40° C. (1 min) @6° C./min to 120° C., @15° C. to 245° C. (5 min)

Carrier: Helium 5.0, 40 cm/s linear velocity, constant flow

MS: Single quadrupole, direct interface, 220° C. inter face temperature

Acquisition: SIM scan mode

Scan parameter: 46-250 amu 6.6 scans/s

SIM Parameter: m/z 60, 74, 6.6 scans/s

m) Glass Transition Temperatures

were determined by dynamic mechanical thermal analysis according to ISO 6721-7. The measurements were done in torsional deformation mode on compression molded samples (40×10×1 mm³) between −130° C. and +160° C. with a heating rate of 2° C./min and a frequency of 1 Hz using TA Ares G2 test apparatus.

n) VOC Content

VOC content was determined according to VDA278 on compositions as directly obtained from compounding, i.e. merely subjected to storage as set forth in VDA 278.

o) Particle Size Distribution of Filler, Particularly Talc

Median particle size d₅₀ and top cut particle size d₉₅ are measured by gravitational liquid sedimentation according to ISO 13317-3.

p) Xylene Cold Soluble Fraction (XCS, Wt.-%):

Xylene cold soluble fraction (XCS) was determined at 25° C. according ISO 16152; first edition; 2005-07-01. The part which remains insoluble is the xylene cold insoluble (XCI) fraction.

q) Intrinsic Viscosity

Intrinsic viscosity was measured according to DIN ISO 1628/1, October 1999 (in Decalin at 135° C.).

r) Ash Content Ash content is measured according to ISO 3451-1 (1997) standard.

s) Density

Density was measured according to ISO 1183-187. Sample preparation was done by compression molding in accordance with ISO 1872-2:2007.

t) Heat Deflection Temperature (HDT):

The HDT was determined on injection molded test specimens of 80×10×4 mm⁻³ prepared according to ISO 1873-2 and stored at +23° C. for at least 96 hours prior to measurement. The test was performed on flatwise supported specimens according to ISO 75, condition A, with a nominal surface stress of 1.80 MPa.

u) DSC Analysis, Melting Temperature (Tm) and Heat of Fusion (Hf), Crystallization Temperature (Tc) and Melt Enthalpy (Hm):

was measured with a TA Instrument Q200 differential scanning calorimetry (DSC) on 5 to 7 mg samples. DSC was run according to ISO 11357/part 3/method C2 in a heat/cool/heat cycle with a scan rate of 10° C./min in the temperature range of −30 to +225° C. The crystallization temperature (T_(c)) was determined from the cooling step, while melting temperature (T_(m)) and melting enthalpy (H_(m)) were determined from the second heating step. The crystallinity was calculated from the melting enthalpy by assuming an Hm-value of 209 J/g for a fully crystalline polypropylene (see Brandrup, J., Immergut, E. H., Eds. Polymer Handbook, 3rd ed. Wiley, New York, 1989; Chapter 3).

v) Shrinkage FD, Shrinkage CD, Anisotropy:

The shrinkage was determined on centre gated, injection molded circular disks (diameter 180 mm, thickness 3 mm, having a flow angle of 355° and a cut out of 5°). Two specimens were molded applying two different holding pressure times (10 s and 20 s respectively). The melt temperature at the gate was 260° C., and the average flow front velocity in the mound 100 mm/s. Tool temperature: 40° C., back pressure: 600 bar.

After conditioning the specimen at room temperature for 96 hours the dimensional changes radial and tangential to the flow direction are measured for both disks. The average of respective values from both disks are reported as final results.

Anisotropy is the ratio of Shrinkage FD versus Shrinkage CD

w) Tiger Stripes (MSE) or Flow Marks

The tendency to show flow marks was examined with a method as described below. This method is described in detail in WO 2010/149529, which is incorporated herein in its entirety. An optical measurement system, as described by Sybille Frank et al. in PPS 25 Intern. Conf. Polym. Proc. Soc 2009 or Proceedings of the SPIE, Volume 6831, pp 68130T-68130T-8 (2008) was used for characterizing the surface quality.

This method consists of two aspects: 1. Image recording: The basic principle of the measurement system is to illuminate the plates with a defined light source (LED) in a closed environment and to record an image with a CCD-camera system.

2. Image Analysis:

The specimen is floodlit from one side and the upwards reflected portion of the light is deflected via two mirrors to a CCD-sensor. The such created grey value image is analyzed in lines. From the recorded deviations of grey values the mean square error (MSE) is calculated allowing a quantification of surface quality, i.e. the larger the MSE value the more pronounced is the surface defect. Generally, for one and the same material, the tendency to flow marks increases when the injection speed is increased.

For this evaluation plaques 440×148×2.8 mm with grain VW K50 and a filmgate of 1.4 mm were used and were produced with different filling times of 1.5, 3 and 6 sec respectively.

Further conditions:

Melt temperature: 240° C.

Mold temperature 30° C.

Dynamic pressure: 10 bar hydraulic

The smaller the MSE value is at a certain filling time, the smaller is the tendency for flow marks.

Experiments

Catalyst System:

For the polymerization process of HECO 1, a Ziegler-Natta type catalyst as used for the inventive examples of WO 2016/066446 A1 and described in detail there was used. For the polymerization process of HECO 2, an identical catalyst but pre-polymerized with vinylcyclohexane to achieve nucleation with poly(vinylcyclohexane) was used.

Nucleation by prepolymerization with vinylcyclohexane is described in EP 2960256 B1 and EP 2960279 B1 in detail. These documents are incorporated by reference. In both cases, triethyl-aluminium (TEAL) was used as co-catalyst and dicyclopentadienyl-dimethoxysilana (donor D) was used as external donor, the respective feed ratios being indicated in Table 1 below.

Heco 1 and Heco 2 were made in prepolymerization/loop reactor/gas phase reactor 1/gas phase reactor 2/gas phase reactor 3 configuration followed by a pelletization step.

TABLE 1 Preparation of HECO 1 and HECO 2 HECO 1 HECO 2 Catalyst As described As described above, above, non- nucleated nucleated Donor D D Prepoly Co/ED mol/mol 8.9 20 Co/Ti mol/mol 220 250 Temperature ° C. 21 20 Residence time min 0.33 0.33 Loop Temperature ° C. 80 70 Pressure kPa 5455 5380 Split wt % 50 40 H2/C3 mol/kmol 6.40 12.0 MFR g/10 min 42 100 GPR1 Temperature ° C. 80 85 Pressue kPa 2600 2670 Split wt % 29 45 H2/C3 mol/kmol 69.3 83.0 MFR g/10 min 42 80 XCS wt % 1.5 2.0 GPR2 Temperature ° C. 80 85 Pressure kPa 2593 2540 C2/C3 mol/kmol 399 400 H2/C2 mol/kmol 84 130 Split wt % 21 15 C2 wt % 25.4 16.0 XCS wt % 20.0 45.0 MFR g/10 min 100 20 Pellet XCS wt % 25.4 16.5 C2(total) wt % 8.1 6.8 C2(XCS) wt % 44.7 38.0 iV(XCS) dl/g 3.7 3.1 MFR g/10 min 20 45 Tm ° C. 165 165 Tc ° C. 127 124

The heterophasic copolymers HECO1 and HECO2 were compounded in a co-rotating twin-screw extruder Coperion ZSK 47 at 220° C. with 0.15 wt.-% antioxidant (Irganox B215FF from BASF AG, Germany; this is a 1:2-mixture of Pentaerythrityl-tetrakis(3-(3′,5′-di-tert. butyl-4-hydroxyphenyl)-propionate, GAS-no. 6683-19-8, and Tris (2,4-di-t-butylphenyl) phosphite, GAS-no. 31570-04-4); 0.05 wt.-% of of Ca-stearate (CAS-no. 1592-23-0, commercially available from Faci, Italy).

Table 2 shows the properties of the polypropylene/polyethylene blends (A) as used for the evaluation.

TABLE 2 Properties of Polypropylene/Polyethylene Blends Mixtures (Blend A) Blend A #2 PP/PE ratio 11:1 Recycling origin Yes, households limonene >0.1 ppm MFR2 (230° C., ISO1133), g/10 min 15.0 Tensile modulus, ISO 527-2, MPa 1260 XCS (wt.-%) 9.0 IV (XCS) (dl/g) 1.0 Charpy NIS +23° C. 5.0 ISO 179 1eA, kJ/m² Charpy NIS −20° C. 2.0 ISO 179 1eA, kJ/m²

TABLE 3 Comparison of the basic properties of HECO 1 and HECO 2 with Blend (A). Blend of HECO1 + HECO HECO HECO2 Blend 1 2 about 1:1 (A) MFR g/10 min 20 45 30 15 Tm ° C. 165 165 165 163 Tc ° C. 127 124 n.d. 123 XCS wt % 8.1 6.8 7.5 9.0 C2(total) wt % 25.4 16.5 21.0 8.5 C2(XCS) wt % 44.7 38.0 41.4 29 iV(XCS) dl/g 3.7 3.1 3.4 1.0 Tens. Modulus MPa 1500 1400 1450 1260 Charpy NIS 23° C. kJ/m² 8.0 6.0 7.0 5.0 Charpy NIS −20° C. kJ/m² 4.5 3.5 4.0 2.0

It can be seen from Table 3 that a replacement of HECO1 and/or HECO2 by Blend (A) was not foreseeable. Blend (A) showed inferior properties with respect to both, stiffness and impact properties.

The HDPE was a commercial grade having a density of 954 kg/in³ (ISO 1183), MFR2 (ISO11133) of 4 g/10 min and a tensile modulus of 850 MPa (ISO 527-2).

The final compositions were compounded in a Coperin ZSK40 twin-screw extruder at 220° C. using the polymers prepared recycled as described above together with talc Jetfine 3CA (d₅₀=1.2 μm; d₉₅=3.3 μm), antioxidants, UV-stabilizers, slip agents, nucleating agents, carbon black masterbatch, calcium stearate, antifogging agent.

IE1 IE2 CE1 HECO 1 wt % 28.45 15.95 40.95 HECO 2 wt % 27.45 14.95 39.95 Blend (A) wt % 25.0 50.0 0.0 HDPE wt.-% 7.0 7.0 7.0 total amount of 9.0 11.2 7.0 polyethylene (HDPE + PE from Blend (A) Talc wt % 10 10 10 Irgafos 168 wt % 0.10 0.10 0.10 Irganox 1010 wt % 0.15 0.15 0.15 Slip agent wt % 0.15 0.15 0.15 (Oleamide) UV-stabilizer wt % 0.11 0.11 0.11 (Chimassorb 119) Nucleating agent wt % 0.09 0.09 0.09 (ADK STAB LA- 408XP) Carbon black wt % 1.50 1.50 1.50 masterbatch (CBMB-LD-09) Density kg/m³ 983 987 977 MFR g/10 min 18.0 14.0 22.0 230° C./2.16 kg Ratio blend (A) vs. — 0.4 1.3 (Heco1 + Heco2) Tens. Modulus MPa 1778 1699 1862 Yield stress MPa 26.0 27.0 25.0 Yield strain % 5.4 7.5 4.0 Stress at break MPa 17.7 8.2 18.8 Strain at break % 17.3 34.6 15.2 Charpy NIS 23° C. kJ/m² 6.1 5.8 6.0 Charpy NIS −20° C. kJ/m² 2.2 2.1 3.1 HDT ISO75 B ° C. 98 91 103 VOC VDA 278. μg/g 66 59 81 pellets Shrinkage FD* % 1.10 1.13 1.10 Shrinkage CD* % 1.34 1.38 1.34 Anisotropy — 0.82 0.82 0.82 Tiger stripes MSE 4 8 6

It can be seen that the impact strength was surprisingly maintained on an acceptable level. The incorporation of the recyclate further resulted in minor stiffness losses. Tiger stripe performance (MSE) was significantly enhanced for lower amounts of recyclate (IE1), whereas VOC (VDA 278, measured on pellets) could be improved significantly (IE1 and IE2). 

1. A composition suitable for automotive application obtainable by blending at least components a) to f), or a), b), c), d), and f) under the proviso that e) is not present a) 12 to 40 wt.-%, preferably 14 to 38 wt. %, more preferably 15 to 35 wt.-% of a first heterophasic polypropylene copolymer (HECO 1) b) 12 to 40 wt.-%, preferably 14 to 38 wt.-%, more preferably 15 to 35 wt.-% of a second heterophasic polypropylene copolymer (HECO 2) c) 15 to 65 wt.-%, preferably 18 to 60 wt.-%, more preferably 20 to 55 wt.-% of a polypropylene-polyethylene blend (A) d) 3.0 to 20 wt.-%, preferably 5.0 to 15 wt.-% and more preferably 6.0 to 15 wt.-% of an inorganic filler e) 0 to 15 wt.-% HDPE f) 0.01 to 4.0 wt.-% of additives wherein all percentages refer to the total composition, and wherein the total content of polyethylene being the sum of said HDPE and the polyethylene of the polypropylene-polyethylene blend (A) ranges from 5.0 to 15.0 wt.-% with respect to the total composition, and wherein (i) the first heterophasic polypropylene copolymer (HECO 1) comprises a matrix phase and an elastomer phase dispersed therein, the first heterophasic polypropylene copolymer (HECO 1) having a melt flow rate MFR2 (230° C., ISO1133) of 8 to 25 g/10 min, preferably 10 to 24 g/10 min, more preferably 12 to 23 g/10 min; and an intrinsic viscosity (measured in decalin according to DIN ISO 1628/1 at 135° C.) of 3.1 dl/g to 4.5 dl/g, preferably 3.2 to 4.4 dl/g, more preferably 3.3 to 4.2 dl/g of the xylene cold soluble fraction (XCS) content; and (ii) the second heterophasic polypropylene copolymer (HECO 2) comprises a matrix phase and an elastomer phase dispersed therein, the second heterophasic polypropylene copolymer (HECO 2) having a melt flow rate MFR2 (230° C., ISO1133) of 25 to 75 g/10 min, preferably 30 to 70 g/10 min, more preferably 35 to 65 g/10 min; and an intrinsic viscosity (measured in decalin according to DIN ISO 1628/1 at 135° C.) of the xylene cold soluble fraction (XCS) content lower than observed for HECO1, preferably 2.0 to 3.2 dl/g, more preferably 2.5 to 3.3 dl/g; and wherein (iii) the polypropylene-polyethylene blend (A) comprises A-1) polypropylene, A-2) polyethylene, wherein the weight ratio of polypropylene to polyethylene is from 19:1 to 7:3, with the polypropylene-polyethylene blend (A) having a melt flow rate MFR2 (230° C., ISO1133) of 5.0 to 30 g/10 min, preferably 7.0 to 26 g/10 min, more preferably 9.0 to 23 g/10 min; and a xylene cold soluble fraction (XCS) of 2.0 to 15 wt.-%, preferably of 2.5 to 13 wt. %, more preferably 3.0 to 11 wt.-% (ISO 16152, led, 25° C.); and optionally a residual ash content of below 3.0 wt.-%, preferably 0.5 to 2.7 wt.-% and more preferably 0.7 to 2.5 wt.-%, and wherein the polypropylene-polyethylene blend (A) has one or more of the following properties (aa) a content of limonene as determined by using solid phase microextraction (HS-SPME-GC-MS) of from 0.1 ppm to 100 ppm, preferably from 0.1 ppm to 50 ppm, more preferably from 0.1 ppm to 20 ppm, most preferably from 0.1 ppm to 5 ppm; (bb) a content of fatty acid(s) as determined by using solid phase microextraction (HS-SPME-GC-MS) of 0.1 to 100 ppm; (cc) a content of polyamide(s) as determined by FTIR of 0.05 to 1.5 wt.-%; (dd) a content of polystyrene(s) as determined by FTIR of 0.05 to 3.0 wt.-%; and wherein (iv) the inorganic filler, preferably talc, has a median particle size d₅₀ before compounding of 0.3 to 3.0 micrometers, more preferably 0.5 to 2.5 micrometers; preferably has a top-cut particle size d₉₅ before compounding of 1.0 to 8.0 micrometers, and wherein the optional HDPE has a melt flow rate (190° C., ISO1133) of 1.0 to 20 g/10 min and a density of 945 to 965 kg/m³ whereby components a) to e) amount to at least 95 wt.-% of said composition suitable for automotive application.
 2. The composition suitable for automotive application according to claim 1 obtainable by blending at least components a) to f), or a), b), c), d), and f) under the proviso that e) is not present in amounts of a) 12 to 40 wt.-%, preferably 14 to 38 wt. %, more preferably 15 to 35 wt.-% of a first heterophasic polypropylene copolymer (HECO 1) b) 12 to 40 wt.-%, preferably 14 to 38 wt.-%, more preferably 15 to 35 wt.-% of a second heterophasic polypropylene copolymer (HECO 2) c) 15 to 65 wt.-%, preferably 18 to 60 wt.-%, more preferably 20 to 55 wt.-% of a polypropylene-polyethylene blend (A) d) 3.0 to 20 wt.-%, preferably 5.0 to 15 wt.-% and more preferably 6.0 to 15 wt.-% of an inorganic filler e) 0 to 15 wt.-% HDPE f) 0.01 to 4.0 wt.-% of additives wherein all percentages refer to the total composition, wherein the total content of polyethylene being the sum of said HDPE and the polyethylene of the polypropylene-polyethylene blend (A) ranges from 5.0 to 15.0 wt.-% with respect to the total composition, and wherein (i) the first heterophasic polypropylene copolymer (HECO 1) comprises a matrix phase and an elastomer phase dispersed therein, the first heterophasic polypropylene copolymer (HECO 1) having melt flow rate MFR2 (230° C., ISO1133) of 8 to 25 g/10 min, preferably 10 to 24 g/10 min, more preferably 12 to 23 g/10 min; and an intrinsic viscosity (measured in decalin according to DIN ISO 1628/1 at 135° C.) of 3.1 dl/g to 4.5 dl/g, preferably 3.2 to 4.4 dl/g, more preferably 3.3 to 4.2 dl/g of the xylene cold soluble fraction (XCS) content; and a xylene cold soluble fraction (XCS) of 19 to 40 wt.-%, preferably of 20 to 37 wt. %, more preferably 22 to 35 wt.-% (ISO 16152, led, 25° C.); and a melt flow rate MFR2 (230° C., ISO1133) of 20 to 50 g/10 min, preferably 25 to 45 g/10 min, more preferably 28 to 44 g/10 min of the xylene insoluble fraction (XCI) (ISO 16152, led, 25° C.), a content of units derived from ethylene in the xylene cold soluble fraction (XCS) of 40 to 60 wt.-%, preferably of 41 to 55 wt. %, more preferably 42 to 50 wt.-%, and wherein (ii) the second heterophasic polypropylene copolymer (HECO 2) comprises a matrix phase and an elastomer phase dispersed therein, the second heterophasic polypropylene copolymer (HECO 2) having a melt flow rate MFR2 (230° C., ISO1133) of 25 to 75 g/10 min, preferably 30 to 70 g/10 min, more preferably 35 to 65 g/10 min; and an intrinsic viscosity (measured in decalin according to DIN ISO 1628/1 at 135° C.) of the xylene cold soluble fraction (XCS) content lower than observed for HECO1, preferably 2.0 to 3.2 dl/g, more preferably 2.5 to 3.3 dl/g; and a xylene cold soluble fraction (XCS) of 8 to 18 wt.-%, preferably of 10 to 17 wt. %, more preferably 12 to 17 wt.-% (ISO 16152, led, 25° C.); and a melt flow rate MFR2 (230° C., ISO1133) of 50 to 200 g/10 min, preferably 60 to 180 g/10 min, more preferably 70 to 160 g/10 min of the xylene insoluble fraction (XCI) (ISO 16152, led, 25° C.), and a content of units derived from ethylene in the xylene cold soluble fraction (XCS) of 25 to 44 wt.-%, preferably of 30 to 42 wt. %, more preferably 35 to 40 wt.-%, and (iii) the polypropylene-polyethylene blend (A) comprises A-1) polypropylene, A-2) polyethylene, wherein the weight ratio of polypropylene to polyethylene is from 19:1 to 7:3, and the polypropylene-polyethylene blend (A) has a melt flow rate MFR2 (230° C., ISO1133) of 5.0 to 30 g/10 min, preferably 7.0 to 26 g/10 min, more preferably 9.0 to 23 g/10 min; and a xylene cold soluble fraction (XCS) of 2.0 to 15 wt.-%, preferably of 2.5 to 13 wt. %, more preferably 3.0 to 11 wt.-% (ISO 16152, led, 25° C.); and optionally a residual ash content of below 3.0 wt.-%, preferably 0.5 to 2.7 wt.-% and more preferably 0.7 to 2.5 wt.-%, wherein the polypropylene-polyethylene blend (A) has one or more of the following properties (aa) a content of limonene as determined by using solid phase microextraction (HS-SPME-GC-MS) of from 0.1 ppm to 100 ppm, preferably from 0.1 ppm to 50 ppm, more preferably from 0.1 ppm to 20 ppm, most preferably from 0.1 ppm to ppm; (bb) a content of fatty acid(s) as determined by using solid phase microextraction (HS-SPME-GC-MS) of 0.1 to 100 ppm; (cc) a content of polyamide(s) as determined by FTIR of 0.05 to 1.5 wt.-%; (dd) a content of polystyrene(s) as determined by FTIR of 0.05 to 3.0 wt.-%, and wherein (iv) the inorganic filler, preferably talc has a median particle size d₅₀ before compounding of 0.3 to 3.0 micrometers, more preferably 0.5 to 2.5 micrometers; and preferably has a top cut particle size d₉₅ before compounding of 1.0 to 8.0 micrometers; and wherein the optional HDPE has a melt flow rate (190° C., ISO1133) of 1.0 to 20 g/10 min and a density of 945 to 965 kg/m³ wherein components a) to e) amount to at least 90 wt.-%, preferably at least 95 wt.-%, most preferably at least 96 wt.-% of the composition suitable for automotive application.
 3. The composition suitable for automotive application according to claim 1 having a tensile modulus (ISO 527.2; 23° C.) of 1650 to 1900 MPa.
 4. The composition suitable for automotive application according to claim 1, obtainable by blending at least components a) to f), or a), b), c), d), and f) under the proviso that e) is not present a) 20 to 40 wt.-%, preferably 20 to 38 wt. %, more preferably 20 to 35 wt.-% of the first heterophasic polypropylene copolymer (HECO 1) b) 20 to 40 wt.-%, preferably 20 to 38 wt.-%, more preferably 20 to 35 wt.-% of the second heterophasic polypropylene copolymer (HECO 2) c) 15 to 30 wt.-%, preferably 18 to 30 wt.-%, more preferably 20 to 30 wt.-% of the polypropylene-polyethylene blend (A) d) 3.0 to 20 wt.-%, preferably 5.0 to 15 wt.-% and more preferably 6.0 to 15 wt.-% of the inorganic filler e) 0 to 15 wt.-% HDPE f) 0.01 to 4.0 wt.-% of additives wherein components a) to e) amount to at least 95 wt.-% of the composition suitable for automotive application.
 5. The composition suitable for automotive application according to claim 1 having a MSE surface quality of below 4.5, obtainable by blending at least components a) to f), or a), b), c), d), and f) under the proviso that e) is not present a) 20 to 40 wt.-% of the first heterophasic polypropylene copolymer (HECO 1) b) 20 to 40 wt.-% of the second heterophasic polypropylene copolymer (HECO 2) c) 15 to 30 wt.-% of the polypropylene-polyethylene blend (A) d) 3.0 to 20 wt.-% of the inorganic filler e) 0 to 15 wt.-% HDPE f) 0.01 to 4.0 wt.-% of additives wherein components a) to e) amount to at least 95 wt.-% of the composition suitable for automotive application.
 6. The composition suitable for automotive application according to claim 1, obtainable by blending at least components a) to f), or a), b), c), d), and f) under the proviso that e) is not present a) 10 to 20 wt.-%, preferably 11 to 20 wt. %, more preferably 12 to 20 wt.-% of the first heterophasic polypropylene copolymer (HECO 1) b) 10 to 20 wt.-%, preferably 11 to 20 wt.-%, more preferably 12 to 20 wt.-% of the second heterophasic polypropylene copolymer (HECO 2) c) 30 to 60 wt.-%, preferably 35 to 55 wt.-%, more preferably 45 to 55 wt.-% of the polypropylene-polyethylene blend (A) d) 3.0 to 20 wt.-%, preferably 5.0 to 15 wt.-% and more preferably 6.0 to 15 wt.-% of the inorganic filler e) 0 to 15 wt.-% HDPE f) 0.01 to 4.0 wt.-% of additives whereby components a) to e) amount to at least 95 wt.-% of the composition suitable for automotive application.
 7. The composition suitable for automotive application according to claim 1 having a heat deflection temperature (ISO 75 B) of at least 90° C.
 8. The composition suitable for automotive application according to claim 1 having a melt flow rate (ISO 1133, 2.16 kg, 230° C.) of 13.0 to 25 g/10 min.
 9. The composition suitable for automotive application according to claim 1 having a VOC as measured on the material as obtained directly from the extrusion following the procedure as described in VDA278 of less than 75 mg per gram of composition.
 10. The article comprising, preferably consisting of the composition according to claim
 1. 11. (canceled) 